3-Metallo substituted naphthalenes

Abstract

3-Prenyl-substituted menaquinones are made by reacting a 3-metallo-2-alkyl-1,4-di(alkoxy or aralkoxy) naphthalene with a prenyl halide, and then oxidizing the resulting 3-prenyl-2-alkyl-1,4-di(alkoxy or aralkoxy) naphthalene to prepare the corresponding 3-prenyl-substituted menaquinone. The metallo substituent at the 3-position may be Li, Li/Cu, Cu or MgBr. The oxidation is advantageously conducted by the use of argentic oxide.

It is claimed: 
     
       1. Compounds of the formula ##STR4## wherein R is lower alkyl and R 1  and R 2  are lower alkyl, or aralkyl of 7 to about 12 carbon atoms, and M is selected from the group consisting of (CuLi) 1/2  and Cu. 
     
     
       2. The compounds of claim 1 wherein R is methyl. 
     
     
       3. The compounds of claim 2 wherein R 1  and R 2  are methyl. 
     
     
       4. A method of preparing lithium-3-naphthyl cuprate of the formula ##STR5## wherein R is lower alkyl, R 1  and R 2  are lower alkyl, or aralkyl of 7 to about 12 carbon atoms, comprising reacting cuprous halide with 3-lithio-naphthalene of the formula ##STR6## in a molar ratio of cuprous halide to 3-lithio-naphthalene of from about 0.3 to 0.7 to prepare the lithium-3-naphthalene cuprate. 
     
     
       5. The method of claim 4 wherein the cuprous halide is cuprous bromide. 
     
     
       6. The method of claim 5 wherein the reaction is conducted with about 0.4 to 0.6 mole of cuprous bromide per mole of the 3-lithio-naphthalene. 
     
     
       7. The method of claim 5 wherein R, R 1  and R 2  are methyl. 
     
     
       8. A method of preparing 3-cupro-naphthalene of the formula ##STR7## wherein R is lower alkyl, R 1  and R 2  are lower alkyl, or aralkyl of 7 to about 12 carbons, comprising reacting naphthyl-3-magnesium bromide of the formula ##STR8## with cuprous halide in a molar ratio of from about 0.9 to 2 moles of cuprous halide per mole of naphthyl-3-magnesium bromide to prepare the 3-cupro-naphthalene. 
     
     
       9. The method of claim 8 wherein R, R 1  and R 2  are methyl. 
     
     
       10. The method of claim 9 wherein the reaction is conducted with about 0.95 to 1.2 moles of cuprous halide per mole of naphthyl-3-magnesium bromide. 
     
     
       11. The method of claim 10 in which the cuprous halide is cuprous bromide. 
     
     
       12. The method of claim 11 wherein the reaction is conducted in the presence of tetrahydrofuran solvent.